JP3141402B2 - Manufacturing method of new energy ray-curable resin - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a novel and useful energy ray-curable resin. More specifically, the present invention provides, as an active ingredient, a specific epoxy compound, a compound having a functional group reactive with a specific epoxy group and an unsaturated double bond, an unreacted isocyanate group and an unsaturated double bond. A method for producing an energy ray-curable resin, characterized by reacting with a compound having the following.

[0002] The energy ray-curable resin of the present invention is suitable for a wide range of uses such as coating materials, printing inks and adhesives, and is extremely useful, which is cured by so-called energy rays such as ultraviolet rays and electron beams. It is possible.

[0003]

2. Description of the Related Art Resins which can be cured by energy rays, in particular, resins which are cured by a radical polymerization reaction, include unsaturated polyester resins, vinyl ester resins (epoxy-acrylates), various oligoacrylates and diallyl phthalate prepolymers. There are various types,
These various resins are widely used in their respective application fields, taking advantage of their respective characteristics.

However, in recent years, as the applications of such resins have been expanded, the demand for their performance has been increasing, but they can be cured by an energy ray which can satisfy all of the various performances. The reality is that the resin composition has not yet been found.

[0005]

SUMMARY OF THE INVENTION However, in view of the above-mentioned circumstances, the inventors of the present invention have found that water resistance, solvent resistance, We have started earnestly studying the synthesis of radical-curable resins with excellent chemical resistance, heat resistance, and curability.

Therefore, the problem to be solved by the present invention is that the energy beam can be hardened at room temperature or freely under heating, and is itself excellent in the curability. In particular, it is an object of the present invention to provide a resin having excellent water resistance, solvent resistance, chemical resistance, etc., and also having excellent heat resistance, which is extremely useful for various applications.

[0007]

Means for Solving the Problems Accordingly, the present inventors have:
Focusing on the problem to be solved by the invention as described above, as a result of diligent and intensive studies, here, a compound containing a specific polyfunctional oxirane ring-containing group reacts with the oxirane ring-containing group A resin obtained by reacting a compound having both a functional group and an unsaturated double bond with a compound having both an unreacted isocyanate group and an unsaturated double bond has excellent curability by energy rays. The present invention has been completed by finding that the above-mentioned various properties of the coating film can be satisfied.

That is, the present invention basically relates to a compound containing an oxirane ring-containing group having a specific structure, a compound having a functional group reactive with the oxirane ring-containing group and an unsaturated bond in the skeleton, It is intended to provide a method for producing an energy ray-curable resin obtained by reacting a compound having both an isocyanate group and an unsaturated double bond in the reaction,

[0009] Specifically, the general formula

[0010]

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Wherein W, X, Y and Z in the formula are
A hydrogen atom or a general formula, which may be the same or different,

[0012]

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(However, all of W, X, Y and Z are excluded when they are all hydrogen atoms.) An oxirane ring-containing compound having a specific structure such that W, X, Y and Z in the compound of formula (I) are a glycidyl ether group or a hydrogen atom (provided that W, X, Y and Z Everything except hydrogen atoms is excluded.)

A reactant with an unsaturated monocarboxylic acid; a polyvalent isocyanate compound; a reactant with a mono- and / or higher poly (meth) acrylate having at least one hydroxyl group per molecule; An object of the present invention is to provide a method for producing an energy ray-curable resin in which an unreacted isocyanate group and a compound having an unsaturated double bond are reacted.

Here, the energy ray-curable resin [hereinafter also referred to as resin (A)]. Is a reaction product of a compound having an oxirane ring-containing group having a specific structure, an unsaturated monocarboxylic acid, a polyvalent isocyanate compound, and a mono- and / or mono- and / or mono-molecular compound having at least one hydroxyl group in one molecule.
Alternatively, it refers to a product obtained by reacting a reactant with a polyhydric (meth) acrylate and / or a compound having both an unreacted isocyanate group and an unsaturated double bond.

As the resin (A), any resin may be used as long as it reacts with the various compounds described above. Of those, only typical ones are exemplified. , First, a specific polyfunctional oxirane ring-containing compound [hereinafter, this is treated as (a-1)]. ] And an unsaturated monocarboxylic acid compound reacting with an oxirane ring-containing group [hereinafter referred to as (a-
Treated as 2). ] (Hereinafter, this will be treated as (a-3)). A mono-isocyanate compound having at least one polyvalent isocyanate compound and at least one hydroxyl group in one molecule.
And / or a compound having both an unreacted isocyanate group and an unsaturated double bond with a polyvalent (meth) acrylate and / or a polyhydric (meth) acrylate [hereinafter referred to as (a
-4). And the like.

Among them, particularly representative examples of the oxirane ring-containing compound (a-1) having a specific structure for preparing the reactant (a-3) are 2,2. 7-dihydroxynaphthalene alone,
Alternatively, β-naphthol is also used in combination therewith, and the compound is converted into an oxirane ring-containing compound via each dimer.

In other words, an oxirane ring-containing compound (W, X, Y) wherein W, X, Y and Z of the compound represented by the aforementioned general formula [1] are each a glycidyl ether group or a hydrogen atom. In all cases, only those in which both Y and Z are hydrogen atoms are excluded).

On the other hand, if only typical examples of the unsaturated monocarboxylic acids (a-2) reacting with the oxirane ring-containing group are given, acrylic acid, methacrylic acid, α-ethylacrylic acid, α-chloroacrylic acid, α-bromoacrylic acid, α-fluoroacrylic acid,
Examples include itaconic acid, crotonic acid, and cinnamic acid, which may be used in combination of two or more, but acrylic acid is particularly preferred.

As typical examples of the polyvalent isocyanate compound for obtaining the above-mentioned compound (a-4), only typical ones may be exemplified, such as 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, A diisocyanate compound having an aromatic ring such as 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, diphenylmethane-4,4'-diisocyanate, 3-methyl-diphenylmethane diisocyanate or 1,5-naphthalenediisocyanate; dicyclohexylmethane Alicyclic diisocyanate compounds such as diisocyanate or isophorone diisocyanate; or aliphatic diisocyanate compounds such as hexamethylene diisocyanate or lysine diisocyanate,

An isocyanate compound obtained by hydrogenating the above-mentioned diisocyanate compound having an aromatic ring, such as hydrogenated xylylene diisocyanate or hydrogenated diphenylmethane-4,4'-diisocyanate; A polyisocyanate compound obtained by subjecting a diisocyanate compound to an addition reaction with a di- to hexavalent low-molecular alcohol represented by trimethylolpropane or the like at a ratio of 2 equivalents of an isocyanate group to 1 equivalent of a hydroxyl group; Or a burette-type polyisocyanate compound obtained by reacting various diisocyanate compounds with water;

Alternatively, 2-isocyanatoethyl-
Trifunctional isocyanate compounds such as 2,6-diisocyanate hexanoate; and multimers obtained by subjecting various diisocyanate compounds to isocyanuration.

Next, only typical representative examples of the functional hydroxyl group-containing (meth) acrylate are given below. 2-hydroxyethyl (meth) acrylate,
2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) Acrylate,

Pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, glycerin mono (meth) acrylate, glycerin di (meth) acrylate, glycidyl (meth) acrylate- (meth) acrylic acid adduct, tris (2 -Hydroxyethyl) isocyanurate-di (meth) acrylate or N-methylol (meth) acrylamide.

These various functional hydroxyl group-containing (meth) acrylates may be used alone or in combination of two or more to obtain the above-mentioned various polyvalent isocyanate compounds (a-4) and NCO equivalent / OH. Equivalent = 1.5-2.0
An unsaturated urethane compound having at least one (meth) acryloyl (oxy) group in one molecule, that is, an acryloyl group, a methacryloyl group, an acryloyloxy group or a methacryloyloxy group, is reacted in a certain ratio. A variety of urethane (meth) acrylate prepolymers are obtained.

As the unsaturated urethane compound or urethane (meth) acrylate prepolymer, only typical ones are exemplified, and examples thereof include reaction products of tolylene diisocyanate and 2-hydroxyethyl (meth) acrylate. .

The compound (a-4) includes, of course,
If only a typical example of a compound having both an unreacted isocyanate group and an unsaturated double bond is exemplified, 2-isocyanateethyl methacrylate and the like can be used. Of course, these may be used alone or in combination of two or more.

The energy ray-curable resin thus obtained has high sensitivity per se, and can give a film excellent in water resistance, solvent resistance, chemical resistance, heat resistance and the like.

The energy ray-curable resin compositions thus obtained, each containing the energy ray-curable resin of the present invention as an essential component, may be added, if necessary, within a range not departing from the object of the present invention. In particular, as long as storage stability and water resistance, chemical resistance, heat resistance, etc. can be maintained, it is possible to add known and customary additives, especially other types of reactive diluents and organic solvents. Nothing is disturbed.

As the reactive diluent, there are widely used monofunctional ones to polyfunctional ones. Among them, only representative ones are exemplified. Hydroxyethyl (meth) acrylate, 2-
Hydroxypropyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, N-vinylpyrrolidone, 1-vinylimidazole, isobornyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, carbitol (meth) acrylate, phenoxyethyl (meth) ) Acrylate, dicyclopentadiene (meth) acrylate, 1,3-butanedi (meth) acrylate,

1,6-hexanediol di (meth) acrylate, polyethylene glycol di (meth) acrylate, hydroxypivalic acid ester neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate pentaerythritol tri (meth) Acrylate, pentaerythritol tetra (meth) acrylate or dipentaerythritol hexa (meth) acrylate.

If only typical solvents are exemplified, aromatic hydrocarbons such as toluene or xylene; ketones such as methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone; methyl acetate, ethyl acetate or butyl acetate; Esters such as;

Alcohols such as methanol, ethanol, propanol or butanol; aliphatic hydrocarbons such as hexane and heptane; cellosolve acetate, carbitol acetate, dimethylformamide or tetrahydrofuran.

The energy ray referred to in the present invention is a general term for ionizing radiation and light, such as electron beam, α ray, β ray, γ ray, X ray, neutron ray or ultraviolet ray. When the resin of the present invention is cured using ultraviolet rays as such energy rays, the wavelength is 1,000 to 8,000.
A photo (polymerization) initiator that can be dissociated by Angstrom ultraviolet rays to generate radicals should be used,
As such a photo (polymerization) initiator, any known and commonly used one can be used.

Among them, particularly representative examples are acetophenones, benzophenone, Michler's ketone, benzene, benzoin benzoate, benzoin, benzoin methyl ethers, benzyl dimethyl ketal, α-acyloxime ester, Thioxanthones, anthraquinones or various derivatives thereof, and the like.

A known and commonly used photosensitizer can be used in combination with such a photo (polymerization) initiator.
Only typical representative examples of such photosensitizers include amines, ureas, sulfur-containing compounds, phosphorus-containing compounds, chlorine-containing compounds, nitriles, and other nitrogen-containing compounds.

The amount of the photo (polymerization) initiator (B) used is
Usually, it may be within a known and commonly used range, preferably within a range of 1 to 3% based on the solid content weight of the resin (A). The energy ray-curable resin and the resin composition containing the same according to the present invention may be usually cured by irradiating radiation or active energy rays by using the above-mentioned energy source as it is.

[0038]

Next, the present invention will be described in more detail with reference to Examples, Comparative Examples, Application Examples and Comparative Application Examples. In the following, all parts and percentages are by weight unless otherwise specified. It is assumed that

Example 1 In a flask equipped with a thermometer, a stirrer and a reflux condenser,
2,7-dihydroxynaphthalene alone or
In addition, β-naphthol was also used, and 556 g of a tetrafunctional epoxy compound obtained through each dimer and 1.3 g of hydroquinone monomethyl ether were charged, and 288 g of acrylic acid and 12 g of triphenylphosphine were added. .8 g and an epoxy equivalent of 15,000.
The reaction was carried out at a temperature of 110 ° C. until the temperature became 0 or more, to obtain a reaction product (a-3-1).

Separately, 1 mol of tolylene diisocyanate and 1 mol of 2-hydroxyethyl acrylate are subjected to a urethanation reaction by a conventional method to obtain an unsaturated isocyanate compound having an unreacted isocyanate group at a terminal (a-4). -1) was obtained.

Next, 844 of (a-3-1) was added to a flask newly equipped with a thermometer, a stirrer and a reflux condenser.
g, 290 g of (a-4-1) were added, and 0.5 g of di-n-butyltin diacetate was added, followed by urethanization reaction at 80 ° C.

It was confirmed by an infrared absorption spectrum analysis (hereinafter, abbreviated as IR analysis) that no isocyanate group remained, and a target energy ray-curable resin was obtained. Hereinafter, this is abbreviated as resin (A-1).

Example 2 In a flask equipped with a thermometer, a stirrer and a reflux condenser,
844 g of (a-3-1) and 580 g of (a-4-1) obtained in Example 1 were charged, and 0.5 g of di-n-butyltin diacetate was added, followed by urethanization at 80 ° C. The reaction was performed.

It was confirmed by IR analysis that no isocyanate group remained, and the desired energy ray-curable resin was obtained. Hereinafter, this is abbreviated as resin (A-2).

Example 3 In a flask equipped with a thermometer, a stirrer and a reflux condenser,
Charge 1 mol of tolylene diisocyanate, and
While paying attention to heat generation, 1 mol of 2-hydroxyethyl methacrylate was added, and the mixture was subjected to urethanization reaction at 80 ° C. to obtain an unsaturated isocyanate compound (a-4-2) having an unreacted isocyanate group at a terminal. .

Instead of (a-4-1), (a-4-
Except having changed to use 304g of 2), it carried out similarly to Example 1, and obtained the target energy ray curable resin. Hereinafter, this is abbreviated as resin (A-3).

Example 4 In a flask equipped with a thermometer, a stirrer and a reflux condenser,
844 g of (a-3-1) and 1,160 g of (a-4-1) obtained in Example 1 were charged, and 0.5 g of di-n-butyltin diacetate was added. A urethanation reaction was performed.

By IR analysis, it was confirmed that no isocyanate group remained, and an intended energy ray-curable resin was obtained. Hereinafter, this is abbreviated as resin (A-4).

Example 5 Instead of (a-4-1), 1,21 of (a-4-2)
A target energy ray-curable resin was obtained in the same manner as in Example 4 except that the amount was changed to 6 g. Hereinafter, this is abbreviated as resin (A-5).

Example 6 In a flask equipped with a thermometer, a stirrer and a reflux condenser,
1 mol of isophorone diisocyanate and 0.1 g of di-n-butyltin diacetate were charged, and 1 mol of pentaerythritol triacrylate was added thereto while paying attention to heat generation, and reacted at 80 ° C., An unsaturated isocyanate compound (a-4-3) was obtained.

Instead of (a-4-1), this (a-4)
-3) except that it was changed to use 1,040 g.
In the same manner as in Example 2, a target energy ray-curable resin was obtained. Hereinafter, this is abbreviated as (A-6).

Application Examples 1 to 6 The following various components were blended with the resins (A-1) to (A-6) obtained in each of the examples, mixed well, and stirred. Each paint was prepared.

Resin (A) 100 parts 1-hydroxyhexyl phenyl ketone 3 parts Trimethylolpropane triacrylate 20 parts

Thereafter, each of the paints thus obtained was applied to a water-sharpened tin plate at a thickness of 20 μm. Next, this was put into a 15 cm
UV light was applied for 60 seconds from the height to cure.

Table 1 summarizes the results of various performance evaluation tests performed on each coated plate. Comparative Example 1 In a flask equipped with a thermometer, a stirrer and a reflux condenser,
"Epiclon N-695" with an epoxy equivalent of 213
426 g of [cresol novolak type epoxy compound manufactured by Dainippon Ink and Chemicals, Inc.] and 1.3 g of hydroquinone monomethyl ether were charged, and 144 g of acrylic acid was added thereto until the acid value became 3 or less. , 1
By reacting at a temperature of 10 ° C., the reactant (c
-3-1) was obtained.

Further, here, 290 g of (a-4-1)
Was added, and a urethanization reaction was carried out at 80 ° C., and it was confirmed by IR analysis that no isocyanate group remained, to obtain a control resin. Hereinafter, this is abbreviated as resin (C-1).

Comparative Application Example 1 In the same manner as in Application Example 1, except that the same amount of the resin (C-1) obtained in Comparative Example 1 was used instead of the resin (A-1), The paint was obtained, applied and cured.

The same performance evaluation was performed on the coated plate, and the results shown in Table 1 were obtained.
The evaluation of each performance was performed in the following manner.

Curability: The applied coating film is cured at 80 ° C.
After drying in hot air for 15 minutes, a 15 cm position was placed under a high pressure mercury lamp having an intensity of 80 W / cm ^2.
It was allowed to pass at a speed of m / min, and the number of times to cure was measured.

Water resistance: The ion-exchanged water is immersed in the gauze, and the degree of decrease in the film thickness after rubbing the cured coating film 40 times is measured. ◎: less than 5 μm ○: 5 μm or more and less than 10 μm △: 10 μm or more and less than 15 μm ×: 15 μm or more Solvent resistance ... Measure.

The evaluation criteria are the same as in the case of water resistance. Alkali resistance: A 10% aqueous solution of sodium hydroxide is immersed in gauze, and the cured film is rubbed 40 times, and the degree of decrease in film thickness is measured.

The evaluation criteria are the same as in the case of water resistance. Heat resistance ............ Apply the applied coating film in hot air at 80 ° C for 1 hour.
After drying for 5 minutes, the cured coating film passed 10 times under a high-pressure mercury lamp of 80 W / cm ² at a speed of 50 m / min under a high-pressure mercury lamp of 80 W / cm ² was heated in a heating furnace at 200 ° C. for 40 seconds. Immediately after placing, the gauze was pressed against the surface of the coating film, the gauze was peeled off after cooling, and the change in the coating film was visually determined.

◎: No change observed at all ：: Some traces of gauze on the surface ×: The coating film was melted and peeled off with the gauze

[0064]

[Table 1]

As is clear from the results shown in Table 1, the energy ray-curable resin composition containing the energy ray-curable resin of the present invention can be freely cured at room temperature or under heating. The properties obtained based on the specific structure of a specific oxirane ring-containing group make it excellent in curability, and the resulting cured coating also has excellent water resistance, solvent resistance and chemical resistance It is known that it is extremely useful for various applications, having excellent heat resistance.

[0066]

The energy ray-curable resin composition containing the energy ray-curable resin of the present invention is itself highly sensitive, and the cured coating film has water resistance, solvent resistance and chemical resistance. It is extremely useful for a wide range of applications such as coating agents and printing inks, in particular, because of its excellent heat resistance and the like.

Claims (2)

(57) [Claims] 1. A compound of the general formula [1] [Where W, X, Y and Z in the formulas may be the same or different, and each represents a hydrogen atom or a formula Represents a group represented by (However, W, X,
This excludes the case where all of Y and Z are all hydrogen atoms. Containing an oxirane ring-containing group represented by)
Is reacted with compound-free, and a compound having both a group and an unsaturated double bond that reacts with the oxirane ring-containing group, and a compound having both a group and an unsaturated double bond that reacts with active Hydrogen
Production of energy ray-curable resin
How . 2. A compound of the general formula [Where W, X, Y and Z in the formulas may be the same or different, and each represents a hydrogen atom or a formula Represents a group represented by (However, W, X,
This excludes the case where all of Y and Z are all hydrogen atoms. )], Wherein at least one oxirane ring-containing group of the compound containing an oxirane ring-containing group has the general formula: [However, R ₁ in the formula and represents a hydrogen atom or a methyl group, R ₂ is assumed to represent a hydrogen atom, a methyl group, a cyano group or a halogen atom, A is to display the acryloyl group or a methacryloyl group, B Is diisocyanate
It is assumed to table the residue. And the other oxirane ring-containing group is a hydrogen atom or a compound represented by the general formula: A group represented by the general formula: Wherein R ₁ and R ₂ are as described above. ]
And / or a general formula: [However, in the formula, R ₁ and R ₂ and A and B are as described above. The method for producing the energy ray-curable resin according to claim 1, wherein the resin is substituted with a group represented by the formula:
Law .